CN-116516351-B - Pickling treatment method for preparing plasma etching resistant passivation film on aluminum alloy surface

Abstract

The invention provides an acid pickling treatment method for preparing a plasma etching-resistant passivation film on the surface of an aluminum alloy, which comprises the steps of carrying out ultrasonic cleaning and blow-drying treatment on a sample in an absolute ethyl alcohol solution, setting an acid pickling flow into four working procedures by taking the mass fraction of diluted nitric acid as a target variable, carrying out oscillation cleaning on the sample in the first working procedure by adopting a constant-temperature water bath kettle at 90-110 ℃ when the solution in the first working procedure contains 595-638ml/L of phosphoric acid, 147-196ml/L of sulfuric acid and 25-55ml/L of nitric acid, carrying out oscillation cleaning on the sample in the second working procedure by adopting the solution in the second working procedure, carrying out oscillation cleaning on the sample in the second working procedure by adopting 441-490ml/L of sulfuric acid and 123-275ml/L of nitric acid, carrying out oscillation cleaning on the sample in the third working procedure by adopting the water in the third working procedure, carrying out oscillation cleaning on the sample in the fourth working procedure by adopting 245-550ml/L of sulfuric acid, carrying out oscillation cleaning on the sample in the fourth working procedure by adopting the solution in the fourth working procedure, and carrying out oscillation cleaning on the sample in the fourth working procedure by adopting the water bath kettle at 18-20 ℃ when the sample is used for cleaning the surface.

Inventors

• FAN HONGQIANG
• ZHU XUAN
• PAN WUJI
• LI FEI
• WANG WEI
• CHEN QINGYE
• LI DINGBIN
• ZHANG XIUXIN
• ZHENG MINZHANG

Assignees

• 上海大学
• 上海恒芯金属制品制造有限公司

Dates

Publication Date

20260512

Application Date

20230411

Claims (3)

1. 1. An acid cleaning treatment method for preparing a plasma etching resistant passivation film on the surface of an aluminum alloy is characterized by comprising the following steps: (1) Processing an aluminum alloy matrix into a sample with a preset shape through wire cutting, ultrasonically cleaning the aluminum alloy by using absolute ethyl alcohol, and drying; (2) Preparing pickling solution, namely diluting nitric acid with water, adding phosphoric acid for mixing, pouring sulfuric acid into the solution, stirring, setting one pickling flow into four working procedures, and mixing the pickling solution of each working procedure according to a certain combination; (3) Sequentially placing the aluminum alloy into four working procedures with different temperatures for swing cleaning, cleaning pickling solution on the surface of the aluminum alloy by deionized water, drying, and vacuumizing for preservation; In the step (2), the combination of the four processes comprises the steps that the first process comprises 595-638ml/L of phosphoric acid, 147-196ml/L of sulfuric acid and 25-55ml/L of nitric acid, the balance of water, the second process comprises 441-490ml/L of sulfuric acid and 123-275ml/L of nitric acid, the balance of water, the third process comprises 595-638ml/L of phosphoric acid and 245-294ml/L of sulfuric acid, the fourth process comprises 245-550 ml/L of nitric acid, and the balance of water, wherein the mass fractions of the nitric acid used in the first process, the second process and the fourth process are the same; In the step (3), the temperature of the four working procedures is that the first working procedure is heated to 90-110 ℃ by adopting a constant-temperature water bath kettle, and the second working procedure, the third working procedure and the fourth working procedure are 18-20 ℃.
2. 2. The pickling treatment method for preparing a plasma etching resistant passivation film on an aluminum alloy surface according to claim 1, wherein in the step (2), the mass fraction of the diluted nitric acid is 20% -40%.
3. 3. The method for preparing a passivation film resistant to plasma etching on an aluminum alloy surface according to claim 1 or 2, wherein in the step (3), the four steps of swinging and cleaning are performed for 40-60 s seconds in the first step and 10-15 seconds in the second, third and fourth steps.

Description

Pickling treatment method for preparing plasma etching resistant passivation film on aluminum alloy surface Technical Field The invention belongs to the technical field of parts of semiconductor etchers, and particularly relates to a method for preparing a plasma etching resistant passivation film by pickling treatment on the surface of an aluminum alloy. Background With the rapid development of the semiconductor industry, miniaturized chips are becoming an indispensable trend at present, which promotes the application of plasma etching technology to semiconductor devices. In etchers, the cavity material plays a critical role in the proper functioning of the machine. In the etching process of the semiconductor device, the mixed gas forms high-energy and active plasmas through ionization, and under a series of physical and chemical actions, the plasmas not only etch the semiconductor device, but also corrode cavity parts of a plasma etching machine prepared by aluminum or aluminum alloy, so that the etching rate of the plasmas to the semiconductor device is reduced, and the service life of the etching machine is shortened. On the other hand, corrosion product particles formed after the cavity part is etched fall on the surface of the semiconductor device to cause pollution, thereby influencing the production quality and efficiency of the product. Currently, the preparation of a plasma etching resistant layer on the surface of an internal part of an etching machine can effectively slow down the corrosion to which the etching machine is subjected. Ceramic materials (such as alumina, yttria, aluminum nitride, etc.) are widely used as plasma erosion resistant coatings due to their high hardness, high temperature resistance, corrosion resistance, good chemical stability, etc. The early preparation method of the plasma etching resistant coating is that alumina is formed on the surface of aluminum through anodic oxidation, but microcracks and holes are easy to appear in the preparation process, so that the plasma etching resistant effect is poor in the service process (thermal spraying technology, 2014,6 (03): 19-23). In addition, wu Shanghua, tan Yicheng et al prepared nano alumina powder into alumina ceramics by high temperature sintering (China, 201610513880.1[ P ]. 2019-03-12). Chen Xiaolong, zhao Hongxu et al spray-coat micro-nano superfine yttrium oxide powder on the surface of aluminum alloy by suspension plasma spray-coating process to prepare yttrium oxide coating (China, 202010796943.5[ P ] 2020-12-11). Defects such as air holes and micro cracks can occur in a coating prepared by high-temperature sintering or spraying and the like, the thermal expansion coefficients of a metal inorganic coating and a substrate material are not matched, the phenomenon of coating falling easily occurs in a plasma working environment, and the semiconductor device in etching equipment is polluted. In addition, the complexity of the preparation process also greatly increases the production time and cost. In the existing pickling technology, a sample is put into pickling consisting of hydrochloric acid, sulfuric acid, phosphoric acid, a corrosion inhibitor, a surfactant, a solution stabilizer and water in CN104611711A 'pickling solution and pickling method of high alloy corrosion resistant steel', and is pickled for 30-40min, washed after pickling, then subjected to nitric acid passivation, subjected to water washing after passivation, and immersed in NaOH or Na 2CO3 solution after water washing. The method has the problems that the pickling time of the sample is too long, and a series of complicated operations such as further washing, passivation, washing and immersing are needed after the pickling. In the prior art CN102965675A, a pickling passivation solution which takes 20 percent nitric acid, 10 percent hydrofluoric acid and 70 percent purified water as a proportion is designed in a stainless steel pickling passivation method, the invention combines the original pickling and passivation steps into one, and the whole pickling passivation process can be summarized into degreasing, flushing, pickling passivation, secondary flushing, alkali liquor neutralization, water washing, tertiary flushing, air drying, sealing, natural air drying and packaging. The method has the advantages of simple process, low cost and low operation intensity, but the whole process is longer and takes longer time, which is not beneficial to industrial production. Disclosure of Invention The invention aims to solve the technical problems, and provides an acid pickling treatment method for preparing a plasma etching resistant passivation film on the surface of an aluminum alloy, wherein an Al 2O3 and AlN composite passivation film is prepared on the surface of the aluminum alloy. The invention provides an acid pickling treatment method for preparing a plasma etching resistant passivation film on the surface of an aluminum alloy, which comprises the foll